1. Field of the Invention
The present invention is directed to composite filters and methods for preparing same. More specifically, it is directed to filter laminates of multiple discrete layers of material bonded together, with at least one of the layers being an asymmetric membrane.
2. Description of the Related Art
Composite filters are filters having multiple layers, and are useful in a variety of separations applications. In many cases, the various layers of a composite filter each impart different desirable properties to the filter. For example, in some applications, an extremely thin membrane may have advantageous flow rates in separations of very small particles, gasses, and the like. Yet such a thin membrane may be fragile and difficult to handle or to package into cartridges. In such cases, the fragile, thin layer membrane may be combined with a backing or with a stronger, more porous membrane, to form a composite having improved strength and handling characteristics without sacrificing the separations properties of the thin layer membrane. Other desirable properties imparted by laminating one membrane to another media may include increased burst strength, increased thickness, providing prefiltration capability, and providing an adhesive layer to ease assembly of a device.
A problem with some composite filters is that the layers may tend to separate in use, adversely affecting the strength and performance of the composite. This problem has been addressed in different ways. In some cases, the layers of desirable composites are laminated together to create bonds between the layers that assist in preventing layer separation (delamination). An example of such a membrane laminate is provided in U.S. Pat. No. 5,154,827. That reference describes a polyfluorocarbon microporous membrane made up of three or more sheets of aggregated microporous fluorocarbon polymer. A fine porosity sheet is laminated between sheets of larger porosity microporous fluorocarbon polymer. A mixing liquid or lubricant is layered between the sheets to facilitate binding and lamination of the sheets to each other, and the stack is laminated into an integral composite membrane under application of heat and pressure. Exploiting the strength provided by the outer layers, the laminate thus formed can be pleated and packaged into filter cartridges.
A different approach to making composite membranes is to cast or form one membrane layer in situ on top of another layer. The base layer may be a fibrous backing material or it may be a membrane. U.S. Pat. No. 5,240,615 discloses a smooth microporous polyvinylidene difluoride (PVDF) membrane laminated to a porous support. A PVDF-containing dope is applied to the porous support and then gelled to form the supported PVDF membrane. A primary advantage for this process, as disclosed in the '615 patent, is that the support prevents shrinkage of the PVDF material during gelling and drying. U.S. Pat. No. 5,433,859 discloses a supported microporous filtration membrane having a support layer with two different zones of microporous membrane being formed thereon. The membrane is made by applying a first casting solution onto the support layer, and then applying a second casting solution on top of the first. Both casting solutions are quenched simultaneously to form the supported membrane. This process forms a continuous, supported microporous membrane with two zones. The fibers of the support layer may penetrate into the adjacent membrane zone, but do not reach the second (top) membrane zone.
One of the primary benefits of composite membranes has been to provide a strong filter material having a relatively low resistance to flow. The greatest resistance to flow occurs in the region with the smallest pores. A composite of a very thin filtration membrane supported by a thicker, more open membrane thus minimizes flow resistance while maximizing strength. In addition, the support material may act as a prefilter, if the support material of the composite is upstream of the minimum pore material. The prefilter effect is especially beneficial in applications requiring a high dirt holding capacity, such as filtration of high particulate solutions, pyrogen removal, sterilization applications, and the like.
The advent of highly asymmetric polymer filters provided an improvement over composites for many applications requiring high flow rate and high dirt holding capacity. U.S. Pat. No. 4,629,563 discloses highly asymmetric microporous membranes with pores on one surface of the membrane having an average diameter 10 to 20,000 times smaller than the pores on the other surface of the membrane. The support layer between the membrane surfaces has flow channels whose diameters generally increase gradually in size along the distance from the minimum pore surface to the maximum pore surface. In the highly asymmetric membranes of the '563 patent and subsequent patents, the smallest pores reside in a relatively thin layer near one surface, and this thin layer of minimum pores thus offers little flow resistance, while the membrane as a whole exhibits the strength and high dirt holding capacity that had previously only been available with composites.
Thus, prior to the present invention, highly asymmetric membranes were seen as a very attractive alternative to composite membranes. The invention disclosed herein represents an advance in composite membrane technology, and a new application for highly asymmetric membranes.